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United States Patent 0
2
1
B. Condensation of 3- or 4-mercaptobenzoic acid with
ethylene chlorohydrin or ethylene oxide followed by
oxidation of the 2-hydroxyethylmercaptobenzoic acid
(e.g. with sodium hydrochlorite or hydrogen peroxide)
to the 2-hydroxyethylsulfonylbenzoic acid.
3,098,096
3- AND 4-(2-CHLORETHYLSULFONYL)-BENZOYL
CHLORiDE
James F. Feeman, West Reading, Pa., assignor to Cromp
ton & Knowles Corporation, Worcester, Mass, a corpo
ration of Massachusetts
In both of these procedures, the aliphatic hydroxyl
may subsequently be replaced with chlorine by treating
No Drawing. Filed June 27, 1960, Ser- No. 38,733
3 Claims. (Cl. 260-544)
This invention relates to a new class of compounds; 10
namely, the meta and para benzoyl chlorides having the
following structure:
the product with concentrated hydrochloric acid at ele
vated temperatures.
The preparation of Structure I compounds from such
intermediates will be described in greater detail in the
examples which appear later in the speci?cation.
.1 and also to meta and para derivatives of Structure I com
‘ pounds which include either of the radicals:
C
/ \
3,098,096
Patented July 16, 1953
(Structure II)
01'
The Structure I compounds can he used to prepare the
Structure II and Structure III type derivatives. In most
instances, a Structure II type derivative is made ?rst and
the Structure III type derivative is prepared from the
Structure II derivative.
Structure II type derivatives are prepared from Struc
ture I compounds by reacting such compounds with a
material which contains a functional group having a hy
drogen which is replaceable under the same conditions
as activate and displace the aroyl chlorine of the Struc
ture I compound, i.e. a functional group which is capa
ble of replacing the chlorine of a carbonyl chloride.
The ‘beta chlorine and the aroyl chlorine of Structure
I compounds have different reactivities; the aroyl chlo
rine ‘being more reactive than the beta chlorine. There
fore, where it is desired to insure the formation of Struc
ture II derivatives without simultaneously forming any
®_soi—cnrpo ru—
0
(Structure III)
appreciable quantity of Structure III type derivatives, it
(In the foregoing structures, and throughout the speci?
is necessary to employ reaction conditions which activate
and displace the aroyl chlorine of the Structure I com
pound without at the same time displacing the beta
chlorine.
Where the functional group of the material to be reacted
/ \
cation, R represents either ——H or -lower aliryl radicals.)
The invention is further concerned with processes for
producing the new Structure I type compounds and the
corresponding derivatives thereof containing Structures II
and III type radicals.
The Structure I type compounds of this invention can
be prepared from the corresponding meta or para sub
with the Structure I compound to form a Structure II de
rivative is at amino group, the reaction can in most in
stances be carried out without signi?cant displacement
stituted intermediates; 2 - hydroxyalkylsulfonylbenzoic 40 of the beta chlorine if the pH of the reaction mass is held
acids or the 2~chloroalkylsuifonyl'benzoic acids. These
intermediates need only be treated with reagents which
will convert the carboxylic acid group to a carbonyl
chloride group in order to form the Structure I com
pounds. Suitable chlorinating agents for this purpose
include thionyl chloride, phosphorus pentachloride, and
the like. With such reagents the alkyl hydroxyl group,
if present, can also be simultaneously converted to the
chloro group. Where the alkyl chloro group is already
present, it, of course, is unaffected by these reagents.
The intermediate Z-hydroxyalkylsulfonyl- or 2-chloro
alkylsulfonylbenzoic acids are compounds which were
heretofore known and may be prepared in various ways.
However, for purposes of simplicity, a description of
the intermediate preparation will be given in rather gen
eral terms and will be con?ned to cases in which R in
Structure I is —H. It will be understood that through
out this application R. may also be -lower alkyl, and
i that compounds wherein R is other than -—H may be
prepared by replacing ethylene chlorohydrin or ethylene
oxide used to form the hydroxyalkylsulfonylbenzoic acids
with an appropriate chloroalcohol such as Z-chloro
propanol, or with suitable epoxy compounds such as
propylene oxide, l,2~butylene oxide, etc. Two routes for
preparing the intermediates are as follows:
A. Reduction of an appropriate (3- or 4-)schlorosulfonyl
benzoic acid to the corresponding sul?nic acid, by
means of sodium sul?te or by means of zinc and acid;
reaction of the sodium sultinate with ethylene oxide
or ethylene chlorohydrin in alkaline solution to pro
duce the Z-hydroxyethylsulfonylbenzoic acid.
at or below about 7. The positioning of the functional
group, the temperature of the reaction mass, and the mole
ratios of the reactants can also in?uence the nature of
the products formed. In all instances, where the position
ing of the amino group is such that its activation will re
quire the employment of reaction conditions which are
somewhat more favorable to the displacement of the beta
chlorine, it is preferred that the molar concentration of
the Structure I compound should equal or exceed the
molar concentration of the material to be reacted to form
the Structure II derivative; this will tend to insure prefer
ential displacement of the aroyl chlorine.
Structure III type derivatives are usually prepared from
Structure II derivatives; however, in some instances it is
possible to go from a Structure I compound to a Structure
III derivative in a single operation without the intermedi
ate formation of a Structure II derivative.
The Structure IlI derivatives are prepared from inter
mediates having Structure II derivatives by reacting such
60 an intermediate with a material which contains a func
tional group having a hydrogen which is replaceable under
the same conditions as activate and displace the beta chlo
rine of the Structure II derivative, i.e. the functional group
of the material must be one which is capable of reacting
with a chloroalklysulfonyl group.
When the functional group on the material to be re
acted with a Structure II intermediate or derivative is an
amino group such as ——NH2 or --NH—, reaction can be
effected under either acid or alkaline conditions. How
ever, care must be taken to avoid carrying out the reaction
under extremely alkaline or extremely acid conditions
which are capable of causing hydrolysis of the amide link
3,098,096
3
age, and the actual pH conditions employed will be de
termined ‘by the stability of the reactants and reaction
products.
When the functional group on the material to be re
acted with a Structure II intermediate or derivative is a
a functional group from which a hydrogen has been dis
placed, and B represents the residue provided by a textile
auxiliary which is capable of ‘forming a hetcrocyclic sys
tem upon condensation with a carbonyl chloride.)
Where it is desired to produce a Structure II type dc
rivative having the following structure:
hydroxyl group, reaction can preferably be effected under
alkaline conditions such as those provided by strong bases.
Sodium hydroxide, trisodium phosphate, and the like are
especially useful as acid binding agents for establishing the
(1:0
desired condition of alkalinity. In most instances the ll)
alkalinity should be comparable to that provided by so
l
(Structure IIn~1)
dium hydroxide solutions containing from about 1/2 to
a Structure I compound is reacted with a textile auxiliary
4% NaOI-I by ‘weight. With many materials which con
having a functional group, such as -—NH2 or —NH— at
tain -OH as functional groups, the reaction will proceed
the desired point of attachment. Generally the reaction
readily at room temperatures; in some instances, how
is carried out under essentially neutral conditions. Acid
ever, it is desirable to accelerate the reaction by heating
binding agents such as sodium bicarbonate, sodium ace
frequently temperatures as high as 100° C. are employed.
tate, sodium carbonate, etc. can be employed to assist in
The upper temperature limit, however, is not critical so
effecting the reaction; however, Where it is intended that
long as the reactants and reaction products are capable
the reaction product be one which is capable of further
of withstanding particular temperatures employed.
reaction with substances or materials having functional
Most natural and synthetic textile ?bers are long chain
groups, the beta chlorine of the chloroalkyl sulfone should
polymers which have functional groups such as —NH-—,
not ‘be replaced, and therefore the pH of the reaction
—NH2 and —OH at various points ‘along the chain. The
should be kept substantially neutral.
cellulosics, such as cotton and viscose rayon are typical
Where it is desired to produce Structure Ila type de
The
‘
textile ?bers with hydroxyls as functional groups.
rivatives in which Z is
cellulosics are not adversely affected to a signi?cant de
gree when treated under alkaline conditions which will
displace the beta chlorine of Structure II derivatives.
Wool, silk and nylon are typical textile ?bers which have
the Structure I type compound is condensed with a com
pound having two functional groups positioned so that a
functional amino groups and such ?bers (sometimes here
in referred to as polyamide ?bers) are relatively stable
heterocyclic ring system is formed; for example, the ortho
under neutral or certain acid conditions which can ‘be em
aromatic diamines and other similar polyfunctional com
pounds containing at least one amino group and which are
ployed to ‘displace the beta chlorine of Structure II de
condensable under neutral conditions to form a hetero
rivatives.
Therefore, the Structure I compounds are useful as re
agents for durably attaching to textile ?bers those mate
rials which can be reacted with Structure I compounds to
‘give Structure II derivatives.
Many presently known textile auxiliaries include amino
groups in their structures at desirable attachment points, 40
or such functional groups can usually be introduced by
appropriate techniques. Many auxiliaries will not per se
react with textile ?bers. Hence, the Structure I com
pounds are useful in the preparation of ?ber reactive tex
tile auxiliaries or for enhancing the ?ber reactivity of iaux
iliaries which have a poor or low order of reactivity.
As used herein, the term “textile auxiliary” is to ‘be
construed as referring to substances used in the dyeing and
?nishing of textiles (e.g. anticrease agents, antifume
agents, antiseptic agents, antislip agents, antistatic agents,
atmospheric-fading protective agents, developers, diazo
bases, dye intermediates, ?nishing agents, ?re and ?ame
resistants, fungicides, germicides, insect repellants (includ
ing rnoth resists), mildew preventatives, mordants, soften
ers, water repellants, optical brighteners, and especially
dyes of all kinds).
When a textile auxiliary which has a functional group
such as ~NH2, —NH—, or the like, reacts with a Struc
ture I compound, different types of Structure 11 deriva
tives are formed which are illustrated by the following
Z
(Structure IIu)
wherein Z represents the meta and para substituent groups
—G-A
(H)
and
(In the foregoing structure, and throughout the speci
?cation, A represents a textile auxiliary attached through
cyclic ring system.
Structure Ila type derivatives will react with materials
having functional hydroxyl and amino groups ‘to produce
derivatives having the structure:
Z
(Structure 11111)
(In the foregoing structure, and throughout the speci?
cation, T represents any material attached through a func
tional group from which a hydrogen has been displaced.
The symbol —f is sometimes used in lieu of —T to desig
nate a textile ?ber which is attached through a functional
group fro-m which a hydrogen has been displaced.)
Where the Structure Ila-l type derivative is a cellulose
reactive, water-soluble dye, the reaction to attach such a
dye to a oellulosic ?ber is usually carried out in an alka
line medium which also contains a migration inhibitor
(such as sodium chloride, sodium sulfate, and the like)
which will prevent the dye from bleeding back in the
alkaline ‘bath ‘before attachment.
According to the invention, it is also possible to use the
Structure 11 type radicals to link two dyes having differ
ent properties and thereby provide a new homogenous
dye of still different character having the structure:
(Structure IIIb)
(A’ and A" representing different dyes, each dye being
attached through a functional group from which a hydro
gen has been displaced.) Thus, for example, a blue dye
can be linked to a yellow dye to give a. green dye.
The Structure I compounds of this invention, as men
tioned previously, are especially useful for preparing tex
tile auxiliaries of Structure II which are then rendered
reactive with various ?brous materials which contain in
their structure, functional or reactive hydroxyl groups or
amino groups and, when so reacted to form Structure III
3,098,096
6
type derivatives, the linkages are stable to stringent Wash
ing conditions, and enable imparting many highly desir
100 parts of benzene is distilled off in similar fashion, to a
pot temperature of 130°, leaving 116 parts of oil. Upon
able durable characteristics to the ?brous materials.
cooling the oil solidi?es to a light colored solid which
melts at 95-7". Recrystallization from benzene gives
Prominent in impontance among the textile auxiliaries
for use in accordance with the present invention are dyes.
After reaction or attachment to textile ?bers, the dyeings
colorless crystalline product melting at 96~7°.
prepared in accordance with this invention possess bright
ness and washfastness to a degree which is unobtainable
with the dyes applied in a conventional manner. As pre
The Preparation of 3-(Z-Chloroethylwlfonyl) ~Benzoyl
viously noted, the Structure I compounds of this invention 10
may be attached to auxiliaries through any suitable func
tional ‘grouping which is capable of replacing the chlorine
groups are present in or can be introduced in a great num
Chloride
Using 3-mercaptobenzoic acid (prepared from a com
mercially available m-aminobenzoic acid) in place of 4
mercaptobenzoic acid in Example 1, gives the correspond
ing 3-(Z-hydroxyethylmercapto)-benzoic acid. The crude
of a carbonyl chloride group, the most important of which
are the amino groups —NH-,, and -—~NH—-. Amino
ber of dyes of different types, e.ig., azo, anthraquinone,
Identi?ed
as 4-(Z-chloroethylsulfonyl)-benz0yl chloride.
EXAMPLE 2
15 product which ‘melts at 70-75 ° is obtained in 70% over
all yield from the m-aminobenzoic acid. Recrystalliza
tion from water raises the melting point to 90-91".
198.2 parts of 3-(Z-hydroxyethylmercapto)-benzoic acid
are dissolved in 1000 parts of water containing 40 parts
basic, diphenylmethane, phthalocyanine, triphenylmeth
lane, nitro, nitrodiphenylamine, etc.
Textile auxiliaries other than dyes may also be con
densed by means of amino groups (or other functional 20 of sodium hydroxide, and oxidized in the manner de
groups present in their structure) with the carbonyl chlo
scribed in Example 1 using 1200 parts of commercial so
ride groups of the compounds of this invention, thereby
dium hypochlorite solution to form 3-(2-hydroxyethy1
imparting to these auxiliaries the possibility of attach
sulfonyD-benzoic acid. The crude product is recrystal
ment, by means of the chloroethylsulfonyl radical, to
Lized from water giving 166 parts of colorless material
?brous and other similar materials which have functional 25 melting at 160-4“. Recrystallization from 95% ethanol
groups that can react with a chloroalkylsulfonyl and dis
gives 138 parts of product which melts at 167~8°.
place the chlorine.
161 parts of pure 3-(Z-hydroxyethylsulfonyl)-benzoic
However, utility of the Structure I compounds as activat
acid, 0.5 part of pyridine, and 350 parts of high-grade
ing and linking reagents is not limited to the textile ?eld;
thionyl chloride are mixed and warmed during 25 hours
they can be used to form bridges or links (as in Structure 30 to 90°, The resultant solution is freed of excess thionyl
ll) between any compatible materials which include func
chloride as described in Example 1 by addition and distil
tional groups of the type described above.
lation of several portions of anhydrous benzene. The oily
The following examples will serve to illustrate the prep
residue weighs 190 parts (theory is 187 parts). Upon
aration of the various compounds and derivatives of this
cooling the product becomes crystalline and then has a
invention. In the examples, unless otherwise indicated, 35 melting point of 5 5—7°. It is very soluble in solvents such
parts are by weight, temperature is given in degrees centi
as benzene and acetone. This has been identi?ed as 3
grade, and percentages are by weight.
(2-chloroethylsulfonyl ) -benzoyl chloride.
EXAMPLE 1
The preparation of 4-(Z-Chloroethylsulfonyl)~Benzoyl
Chloride
154.2 parts of 4-rncrcaptobenzoic acid are dissolved at
35° in 1500 parts of water containing 100 parts of sodium
hydroxide, and treated dropwise in 30 minutes with 85
40
EXAMPLE 3
Twelve parts of 7-amino-1-naphthol-3-sulfonic acid are
dissolved at pH 7.5 by means of three parts of sodium
carbonate in 100 parts of Water, and with vigorous stirring,
there are added 8 parts of sodium bicarbonate and a solu~
tion of 14 parts of 3-(Z-chlorocthylsulfonyl)~benzoyl chlo
parts of ethylene chlorohydrin. After stirring 15 minutes 45 ride in 20 parts of acetone. Reaction is complete in a
few minutes. The resultant solution contains the com
longer, concentrated hydrochloric acid is added until the
pound of the structure:
pH is 1.5, and the nearly quantitative, colorless precipitate
of 4-(Z-hydroxyethylmercapto)-benzoic acid is ?ltered,
washed with cold water and dried. The crude material
melts at 146—8°; recrystallization ‘from water raises the 50
melting point to 151-3".
198.2 parts of 4-(Z-hydroxyethylmercapto)-benz0ic
acid are dissolved in 1000 parts of water containing 40
parts of sodium hydroxide. At 20° 1200 parts of com
mercial sodium hypochlorite solution (12.4% NaOCl) are 55
This solution may be used directly for application to
[added dropwise during two hours. The solution is
?brous materials as a developer for any suitable free or
warmed during one hour to 45°, and in 45 minutes longer
stabilized diazonium salt as set forth in Example 4. It
to 70°, when the presence of sodium hypochlorite is no
may also be used in solution as a coupler in the manu
longer detectable with starch-iodide paper. The solution
facture of reactive dyes. The compound can be isolated
is cooled externally to 20°, hydrochloric acid is added to 60 by salting, dried, and used subsequently as a coupler or
pH 1.5, and the colorless crystalline precipitate of 4-(2
developer.
hydroxyethylsulfonyl)-benz.oic acid is ?ltered. The crude
EXAMPLE 4
product is puri?ed from water by recrystallization giving
163 parts (71% of theoretical) of product which melts
A solution of one part of the product of Example 3
at 185-9”. Recrystallization from 95% ethanol gives 100 65 in 50 parts of water at 25° is used to impregnate a
parts of pure material melting at 193-4".
piece of spun rayon ‘fabric; the ‘fabric is dried; “and it is
then impregnated with a 1% sodium hydroxide-30% so
dium chloride solution in water. The fabric is cured
for ?ve minutes at 105°, rinsed well in water, rinsed in
mixture is slowly warmed to 90° (during three hours), 70 1% sodium bicarbonate solution in water, and scoured at
the boiling point in water containing 0.1% of a non
becoming quite viscous at ?rst, but ?nally giving a clear
solution. After heating at 90° for 1.5 hours longer, the
ionic detergent (Triton X-100, a non-ionic surface active
agent manufactured by Rohm & Haas Company). The
solution is cooled to 75°, 100 parts of benzene are added,
and the benzene-thionyl chloride mixture is distilled off to
fabric is rinsed and dried, and now has a pale straw color,
a temperature of 95° in the pot. A second portion of 75 which changes to yellow in alkaline solution. The fabric
93 parts of pure 4-(Z-hydroxyethylsulfonyl)-benzoic
acid and 0.5 part of pyridine are treated with 180 parts of
high'grade thionyl chloride at 30° in ten minutes. The
3,098,096
8
d
well, the fabric is placed in an ice-cold bath containing
is cut into three pieces and developed in cold 5% sodium
carbonate solution by addition of solutions of the fol
lowing diazonium salt to the individual pieces to give
excess nitrous acid, and allowed to‘ remain there ten
minutes. The fabric is then rinsed in cold water, out
into a number of pieces, and the pieces introduced indi
vidually into alkaline solutions containing excess amounts
very wash ‘fast colors as follows.
Diazonium salt solution ‘from:
of water-soluble developers. The following table gives
some of these developers and the colors they furnish,
Metanilic acid ______________________ __ Scarlet.
4-methoxymetanilic acid ______________ _. Red.
which are very ‘fast to washing, and have good to excellent
5 - amino-?-methoxynaphthalene-2-sulfonic
acid ____________________________ __ Violet.
fastness to light.
10
EXAMPLE 5
Developer:
Color
Barbituric acid ______________________ _. Yellow.
3 - methyl - l-(p - sulfophenyl)-pyrazol—5
24 parts of 7-amino-1-naphthol-3-sulfonic acid, dis
solved in 200 parts of water at 30° with 6 parts of so
dium carbonate, is treated with 16 parts of so
dium bicarbonate and then with vigorous stirring with a
Resorcinol _________________________ __ Orange.
solution of 28 parts of 3-(2-chloroethylsulfonyl)-benzoyl
6-amino-1-naphthol-3-sulfonic acid _____ ._. Scarlet.
chloride in 40 parts of acetone. After five minutes, the
resultant solution is iced to 15° and 20 parts of sodium
bicarbonate is added. Meanwhile a neutral solution of
21 parts of 4-methoxymetanilic acid is acidi?ed with 25 20
S-amino-l-naphthol-3,6-disulfonic acid ____ Maroon.
one _____________________________ __ Yellow.
3-hydroxy-naphtl1anilide _____________ __ Red.
EXAMPLE 9
at 0° with a solution of 7 parts of sodium nitrite in 25
‘parts of water. This diazonium salt solution is added
A neutral solution of 2,5-diarninobenzenesulfonic acid
(9.4 parts) in 100 parts of water at 40“ is treated, while
stirring vigorously, with a solution of 14 parts of 3-(2
chloroethylsulfonyl)-benzoyl chloride in 25 parts of ace
slowly with good stirring to the coupler solution at pH
tone.
7.0 to 7.5 and at 10°.
acylated completely, the pH of the solution is lowered to
5 with acetic acid and the product is separated. It is
parts of concentrated hydrochloric acid and diazotized
After one hour the pH is lowered
to 5.0 with 20 parts of ‘acetic acid and the solution (800
parts) is treated with 80' parts of sodium chloride. The
‘then diazotizcd at 0° in the presence of excess hydro
chloric acid with a solution of 3.5 parts of sodium ni
trite. Addition of the diazonium salt to a neutral solu
precipitated red dye is ?ltered and dried in vacuo, giving
83 parts of dye which is reactive with cellulosic ?bers
and has the structure:
OCIIa
30
tion of 12.7 parts of 3-methyl-1-(4-sulfophenyl)-pyrazol
5-one in 250 parts of water containing 15 parts of so~
OH
‘
H038
When the more basic S-amino group has been
dium bicarbonate, gives a yellow solution, ‘from which
the dyestu?i of the formula
if
HOgS-
-— CHI
GitC~N—C>—N=N
|
ii
OrOHa-CHi-Cl
oi-om-oni-soi
EXAMPLE 6
H
/
SOzNa no
18 parts of metanilic acid, a new reactive dye is obtained
having the following structure and dyeing cellulosic ?bers
scarlet shades of excellent wash fastness and good fastness
to light.
N=N—
sour
t
—NH—C
riots-
SOrCHrCIIz-Cl
EXAMPLE 7
A neutral solution of 18.8 ‘parts of 2,5-diaminoben
zenesulfonic ‘acid in 200 parts of water at 40° is stirred
vigorously and treated with a solution of 27 parts of 4—
(2»chloroethylsulfonyl)-benzoyl chloride in 100 parts of
acetone. After completion of the reaction, the pH is
lowered to 5 with acetic acid and the colorless crystalline
product ?ltered. It has the structure:
/
l
In Example 5, while otherwise proceeding as described,
it the 21 parts of 4-methoxymetanilic acid is replaced with 40
0H
N
N
SOsNa
is separated by addition of 125 parts of sodium chloride.
The ?ltered crystalline dye is dried in vacuo at 30°, and
is reactive with cellulosic ?bers giving washfast and light
fast yellow shades.
EXAMPLE 1O
50
Eleven parts of ‘the monoazo dye obtained by alkaline
coupling of diazotized Z-amino-l-phenol-4-sulfonic acid
and 6-arnino-l-naphthol-B-sulfonic acid is dissolved in 200
parts of water. It is coppered by adding 4.5 parts of
anhydrous sodium acetate and a solution of 6.5 parts of
CuSO4.5H2O in 25 parts of water, and heating at 90° for
one hour. The solution obtained is made slightly al
kaline with sodium carbonate and clarified from a small
amount of insoluble matter.
It is then treated at 40°
60 and pH 7.0 to 7.5 in the presence of 4 parts of sodium
bicarbonate with a solution of 7 parts of 3-(2-chloro
ethylsulfonyl)~benzoyl chloride in 20 parts of acetone.
The ‘resultant solution is ‘salted 5% by volume with so
This dye intermediate may be applied directly to ?brous
materials or used as an intermediate and converted into
‘reactive dyes ‘by diazotization and coupling reactions.
EXAMPLE 8
A solution of one part of the product of Example 7
in 50 parts of water at 25° is padded onto a piece of spun
rayon ‘fabric. The fabric is dried, impregnated with 1%
sodium hydroxide-30% sodium chloride solution in
water, cured in the oven ‘at 105°, rinsed in water, then in
dium chloride at pH 5 giving a crystalline precipitate
which is ?ltered and dried in vacuo.
The new dye is re
active with cellulose giving bluish~red shades of excellent
fastness to both light and Washing.
EXAMPLE l1
3-nitro-4-chlorobenzenesulfonic acid (23.8 parts) as a
neutral solution in 400 parts of water is mixed with 25
parts of sodium carbonate and 12 parts of p-phenylenedi
amine, and the mixture heated at 90° for two hours.
The yellow-brown solution which is produced is ?ltered,
1% sodium bicarbonate solution, and scoured at the boil
with water and 0.1% non-ionic detergent. After rinsing 75 and the product isolated by acidi?cation with hydrochloric
3,098,096
10
(prepared by condensation of 2,5 -diaminobenzenesulfonic
acid with 1-amino-4-bromoanthraquinone-Lsulfonic acid)
acid. The product is then dissolved in 400 parts of water
at pH 7.5 by means of sodium carbonate, and treated
with 30 parts of sodium bicarbonate, followed by a
in 1200 parts of water with 40 parts of sodium bicarbond
etc is treated at 55° with a solution of 35 parts of 4-(2
solution of 23 parts of 442-chloroethylsulfonyl)-benzoyl
chloride in 100 parts of acetone. The reddish-yellow
product precipitates and is ?ltered, washed once with 50
parts of water, and dried in vacuo. Viscose rayon padded
in a solution of the product in water at 80°, dried, treated
with a 1% NaOH—30% NaCl solution, cured at 105°,
and washed in water containing a non-ionic detergent 10
(Triton X-100), is dyed a wash fast and light fast orange
yellow shade.
EXAMPLE 12
chloroethylsulfonyl)-benzoyl chloride in 100 parts of
acetone. The mixture is stirred two hours at 40 to 50°,
the pH lowered to 5 with acetic acid, the blue dye salted
out, ?ltered, and dried in vacuo. It dyes cellulosic ?bers
in bright blue shades which are fast to light and washing.
EXAMPLE 15
One part of the dye obtained in Example 10 is dissolved
in 100 parts of water. A cotton fabric is impregnated
with the solution thus prepared to an increase in weight
A solution of 71.4 parts of the compound of the for 15 of 100% , and dried. The fabric is then impregnated with
a solution at 25° containing 1% sodium hydroxide and
mula
30% sodium chloride, squeezed to an increase in weight
of 100%, steamed for three minutes at 100° to 105°,
NH:
rinsed, washed for ten minutes in a 0.2% boiling solution
SO3Na
20 of Triton X-l00, rinsed and dried. A bright bluish-red
dyeing is obtained which has excellent fastness to wash
ing and to light.
SOaNa
EXAMPLE 16
NH:
5,6-diamino-l-naphthol-3-sulfonic acid (25.4 parts) is
25 dissolved as the sodium salt in 200 parts of water and then
EQaNa
treated with 20 parts of sodium bicarbonate and a solu
tion of 28 parts of 4-(2-chloroethylsulfonyl)-benzoyl
(prepared by condensation of 1-amino-4-bromo-anthra
quinone-Z-sulfonic acid with 4,4'-diaminobiphenyl-2,2’
chloride in 100 parts of acetone. The resultant solution
is then coupled in the presence of excess sodium bicar
sodium bicarbonate at pH 7.5 is treated at 50° with a 30 bonate with a diazonium salt solution obtained from 17.3
disulfonic acid) in 600 parts of water and 20 parts of
parts of metanilic acid, giving a red dye which is reactive
with cellulosic ?brous material of good light and washing
fastness. The dye has the probable constitution:
solution of 28 parts of 3-(Z-chIoroethylsulfonyl)-benzoyl
chloride. After 30 minutes the pH is lowered to 5.0 with
acetic acid, and the product is isolated by salting and dried
H035
N=N—
__
N=o-Osoi-cni-oni—oi
l
N
01H
11
EXAMPLE 17
in vacuo. It is a blue solid which is reactive, giving blue
dyeings which are fast to light and washing.
EXAMPLE 13
77.1 parts of the compound of the formula
S OaNa
It
, One part of reactive dye prepared according to Example
6 is dissolved in 1000 parts of water at pH 5 and 100°;
a wool fabric weighing 50 parts is entered into the bath
and agitated thoroughly. After ?fteen minutes, one part
of acetic acid is added and agitation is continued for 45
minutes at 100°. The fabric is removed, rinsed and dried.
It is dyed a brilliant red shade and the color has excellent
50 fastness to washing and good fastness to light.
When 50 parts of a nylon fabric is used to replace the
50 parts of wool fabric of the preceding example, the
4
nylon is dyed similarly and the color has similar fast
(prepared according to the procedure outlined in US.
' ness properties.
Patent 2,795,577, Example 6), in 1600 parts of water and 55
28 parts of sodium bicarbonate is treated with 28 parts
of 4-(2-ch1oroethylsulfonyl)-benzoyl chloride in 100
EXAMPLE l8
parts of acetone at 50". After thirty minutes the solution
is ?ltered and 350 parts of sodium chloride added. The
crystalline precipitate is isolated by ?ltration and dried in 60
vacuo. The product in aqueous solution ?uoresces bright
green-white under ultraviolet light, and reacts with cellu
losic ?bers imparting optical brightness which is fast to
Forty-one parts of the compound of the formula:
0
NH:
washing and light.
803K
EXAMPLE 14
65
A neutral solution of 53.3 parts of the compound of
the formula
?
8)
SOaNa
70
,0
N
NH,
SO3Na
is dissolved at pH 7.5 in 1000 parts of water at 40°, 20
NH:
parts of sodium bicarbonate is added, and then a solution
75 of 28 parts of 3-(2-tchloroethylsulfonyl)-benzoyl chloride,
3,098,096
11
12
dissolved in 40 parts of acetone, is added. The prod
after a few minutes.
uct having the structure:
compound of the formula:
(|)
Then a solution of 41 parts of the
NH:
80211
10
at pH 7 in 600' parts of Water is added, and the resultant
solution is heated to 100° and held there for four hours.
A solution of 25 parts of copper sulfate pentahydrate in
100 parts of Water is added carefully and the resultant
slurry heated one hour more. The resultant green dye is
?ltered and dried. It dyes natural ‘and synthetic poly
amide ?bers in bright green shades, ‘and is the copper com
plex of the dye of structure:
precipitates. The pH is lowered to 5 with acetic acid,
the blue dye is separated by ?ltration and dried in vacuo.
It dyes wool, nylon, silk ‘and other polyamide and pro
teinaceous ?bers in red-blue shades having good fastness
to light and washing.
EXAMPLE 19
One part of the dye prepared in Example 18 is dissolved
SIOaH
Oz—CH:—CHg—1l\1'—®—L|*-————
H
0.
in 1000 parts of water at pH 6.5 and 100°, and a nylon
fabric weighing 50 parts is entered. The fabric is agi
tated in the solution tor one hour at 100°, rinsed and
dried. It is colored ‘a navy-blue shade which is of very
good washing and light ?astness.
NH,
H
=0
I claim:
1. A compound having the following structure
H
45
R
R1—SO2——(JJ—+—-C1
R R
wherein R is a radical selected from the group consisting
of -—H and -lower alkyl and R1 is a radical selected from
EXAMPLE 20
‘the group consisting of
The compound (42 parts) of the formula:
g
and
55
0:0
61
60
2. 3-(2-chloroethylsulfonyl)-benzoyl chloride.
3. 4-(2-chloroethylsulfonyl)4benzoyl chloride.
References Cited in the ?le of this patent
UNITED STATES PATENTS
65
is dissolved at neutral pH in 600 parts of Water at 25°
and treated successively with ‘good stirring with 40 parts
of sodium bicarbonate and a solution of 28 parts of 4
(2-chloroethylsulfonyl)-benzoyl chloride in 150 parts of
acetone.
No free ‘aromatic amino groups are present
70
1,342,134
Schedler ______________ __ June 1, 1920
2,022,243
2,339,739
2,670,265
2,743,267
2,895,785
2,919,269
2,929,673
2,975,167
2,995,412
Lange _______________ __ Nov. 26,
Blackshaw et a1. ______ __ Jan. 18,
Heyna et a1 ___________ __ Feb. 23,
Heynia et a1. __________ __ Apr. 24,
Alsberg et a1 ____________ __ July 21,
Nickel et a1. _________ __ Dec. 29,
Sehucan _____________ __ Mar. 22,
Schwander et al _______ __ Mar. 14,
Kleb ________________ __ Aug. 8,
1935
1944
1954
1956
1959
1959
1960
1961
1961
13
a
a,
a
1“
UNITED STATES PATENT OFFICE
;
CERTIFICATE OF CORRECTION
Patent No. 3,098 ,696
July 16, 1963
James F. Feeman
It is hereby certified that error appears in the above numbered pat
ent requiring correction and that the said Letters Patent should read as
corrected below.
Column 1, line 36, for "Structures" read —— Structure ——;
column 2, line 4, for "hydrochlorite" read —— hypochlorite ——;
j
‘
line 65, for "chloroalklysulfonyl" read —— chloroalky-lsu-lfonyl
—-' column 3, lines "(I to 73, the formula should appear as
shown below instead of as in the patent:
columns 11 and 12, in the formula at the center of the page,
the upper left-hand portion of the formula reading:
HO
Signed and sealed this 21st day of January 1964.
(SEAL)
Attest:
ERNEST W. SWIDER
Attesting Officer
EDWIN L.‘ REYNOLDS
Acting Commissioner of
Patents
‘
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent; No. 3,098,096
J uly 1h, 1963
James F. Feeman
corrected below.
Column 1,
line 36,
for "S Lruc Lu res" read —— Struc Lu re ~— ;
column 2, line 4, for "hydrochlori te" read —— hypochlori te ——;
line 65, for "chloroali:lysuli‘onyl" read —— chloroalkylsulfonyl
——; column 3, lines ‘71 to 73, the formula should appear as
shown below instead of as in the patent:
-c
/
2
columns 11 and 12, in the formula at the center of the page,
the upper left-hand portion of the formula reading’:
read
HO
Signed and scaled thi 5 215 t day of January 1904 .
(SEAL)
At
Lest: W. SWIDER
ERNEST
Antes Ling Officer
EDWIN} L. REYNOLDS
Acting Commissioner of
Patents